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CARL ROTH, OF CHARLOTTENBURG, BRUSSIA,-ASSlGNGR TO LUDW. LOEWifl & 00. COMMANDIT-GESELLSGHAFT AUF AGTIEN, 3F BERLIN, GERliL-XNY.

exerc sers.

EPECIFICATION forming part of Letters Patent No. 375,651, dated December 27, 1887.

Afaplication filed July 25. 1887. Serial No. 245,251.

(No specimens.) Patented in Germany April 20,1886,No. 39,511; in Franco July 9, 1856, No.-177,309; in England July 14, 1886. No. 9,166,21nd February 21, 188?,1'l'o. 2,679; in Belgium August 2, 1886, No. r 74,010; in Luxcmhurg August 5, 1886, No. 718; in Sweden August I, 1886, No. Bliicnd in Norway August 19, 1886, No. 288.

To aZZ whom it may concern:

Be it known that I, CARL ROTH, doctor of philosophy, subject of the Grand Duke of House, and resident at )harlottenburg, near 5 Berlin, Kingdom of Prussia, Germany, have invented certain new and useful improvements in the Manufacture of Explosives, (for which 5 I have obtained Letters Patent in France July 9,1886, No. 177,309; in Great Britain July 14, 1o 1886;1lo. 9,166; in Belgium AugustZ, 1886, No. 74,074); in Luxemhurg August 5, 1886, N0. 718; in Norwuyeugust 19, 1888, No. 288; in Sweden August 7, 1886, N o. 885; in Germany April 20,

. 1886, No. 39,511, and in Great Britain Fem-u ary 21 1887, No. 2,679,)01. which the follow- 'ing is aspecificction. My invention relates to the manufacture of ,3 explosives from aromatic hydrocarbons and mixtures thereof, such as benzol, tolnol, phe- 5 mil, cresol, (cresylic acid,) and nuphthalihe,

1 either derived from coal-tenor from other sources, fractional products of coal-tar in generel,"as also coal-tar itself; and it consists'in Combining with oxygen yielding substances 25 compounds prepared with said products by iucornorating thereinto hot-h chlorine and one or more nitro groups, and also in providing means for properly regulating the notion of such explosives. 36 Ofthc carbon compounds which,when mixed with oxygen-yielding substances, form explosives, only the nit-rated hydrocarbons end by droxyl compounds of the aromatic group and certain sulpho-acids have hitherto been employed. (\Vith reference to the nitro C0331- pounds as components of explosives, see Sprengel on a new class of explosives which are non-explosive during their manufacture, storage, and transport," and the Bulletin do 0 lasocit Chimiqne Francoise, 1873, XX,

No. 10, p. 257, and with regard to the sulphoire-ids see Bockmaun, .Explosiv-Stoti'e, p. 207, note.) No use, however, has heretofore been made for the same purpose of aromatic a, compouuds containing both nitro groups and chlorine.

The advantage obtained by the introduction of chlorine as Well as nitro groups into bencol, toluol, phenol, cresol, (cresylic acid,) and by the chlorine when set 1 nephthalinjractional products of c0al-ter in general, as also in thecoal-taritself, is that the chlorine exerts a loosening effect on the nitro groups, and accordingly enables the said groups to react more readily on the oxygenyielding snbstanccs thet is to say, it enables 5 5 the compound to burn morereadiiy than when nitro groups only are present. As has been proved by numerous experiments, the dynamic edect is also considerably increased by the introduction of chlorine into the nitro com- 6o pounds, probably in consequence. of the in crease in the volume of the combustioug'eses ree..' V Compounds constituted as aforesaid, or mixtures of such compounds with each other, are

obtained either by nitreting chlorutcd sub stances or bychlorating-nitro products, or by the action of agents which produce it nitrating and e chlorating cflect at the some time, preferably of a mixture of nitric and hydro- 7o chloric acids. And in order to give a guidonce to those skilled in the art to which my invention relates, I will now proceed to describe as examples some ways of producing such. aromatic chlornitroproducis 75, First example: (lne purtof bcnzol-chloride is gradually introduced into a. mixturecomposed of three parts of highly-concentrated nitrio acid of 1.52 specific gravity and six parts of concentrated sulphuric acid, the vessel being artificially cooled during the operation, if required, and after the evolution of nitrous vepor has ceased the reaction is completed by the application of heat. After the addition of water a crystalline product separates out,.- which, according to the degree of purity oi the beuzol-chloride, has e color varying between yellow and brown. This product is cleansed from the adhering acid by washing with a. copious quantity of Water, and afterword drle- Second example: Chlorine is introduced into phenol, heated to 50 centigrade, until the weight is increased by one-half. The semifluid crystalline mass is then introduced in 5 small portions into three times its weight of nitric acid of 1.4 specific gravity, the vessel being cooled during the operation.

The

of five parts of nitrate ofsoda and six parts -l concentrated sulphuric acid, and, after the most violent reaction is concluded, is gently heated with this mixture during three to four h urs. One part of the washed yellowish yrown product having then been carefully fixed with 0.8 part of chlorate of potash, five parts of concentrated hydrochloric acid are allowed to How by degrees into the mixture, and a gentle heat is applied to the vessel. The final product is freed from the adhering salt by washing with water, and dried, and then forms an easilyunelting orange-yellow crystalline mass of about 1.4 specific gravity.

Fourth example: Twelve parts of nitric acid of 1.45 specific gravity are heated with four parts of sodium chloride during about one hour, to from to centigrade, and sub" sequcntly cooled. Two-parts of naphthaline in small portions are then added to the mixture, and toward the conclusion of the reaction the whole is geutlyheatcd. The reddish mass which separates out, having been freed from salt by washing, is introducedinto three parts of nitric acid of 1.52 specific gravity and six parts ofconcentratedsulphuric acid and digested with the acid mixture for several hours. The brownish-yellow product obtained after treatment with water is of a crystalline nature and of a specific gravity of about 1.4.

Fifth example: Four parts of the fractional distillate of coal-tar which goes over at a temperature of between 190 and 210 centigrade are gradually introduced into a. mixture composed of ten parts of nitric acid of 1.4 specific gravity and five parts of hydrochloric acid oftwenty-fourpercent, the vessel being cooled during the operation. One part of the oily product, which after a time becomes crystalline, is gradually incorporated into a mixture composed of three parts of nitric ac d of 1.52 specific gravity-and seven parts of concentrated sulphuric acid, and the reaction is completed by heat. The product obtained, after washing and drying, forms a brown greasy mass, becoming crystalline at about 10 centigrade.

Sixth emmple: Five parts of coal-tar are caused to How in a fine stream or jet into a mixture composed ofiil'toen parts of nitric acid of 1.45 specific gravity and twelve parts of hydrochloric acid at tweutyd'our per cent.

ceased, the reaction is promoted by he One art of the plastic productv of the re;

then introduced into a mixture of five parts of nitric acid of 1.52 specific gravity and fifteen parts of sulphuric acid and digested with the acid mixture for several hours. The final produet obtained, after washing and drying, forms a brown amorphous powder.

The analysis of the product obtained accord ing to the last example shows the proportion ofchlorine contained therein to be 8.3 per cent. The proportion in the other products varies from ten to twenty-one per cent.

In order to produce the explosive matter, one part of the said chlorated and nitrated compounds is mixed, according to the quan ti ty of carbon and of hydrogen present therein, with from two to five parts of oxygen-yielding substances, preferably with niter in its various formsforinstance, with uitrateofsoda, of potash, or of ammonia. Especially powerful effects have been obtained with the mixture of one part of the chloronitro compound produced according to example four with two parts of nitrate of potash.

As before mentioned, explosives combined in the manner described possess the property of very rapid combustion in exploding, and, besides, require a strong flame or flash, such as that produced by fulminate of mercury. in order to render them fit for use where it is desired to have a less sudden or violent action, and, moreover, to permit them to easier explode, I may proceed as follows:

To the blasting-mixture consisting'of chlornitro (chloratedand nitrated) products and substances yielding oxygen Iadd a small percentage of sulphur. This sulphur diminishes the suddenness or rapidity of the explosion, and, moreover, augments the heaving or splitting action on the one hand, and on the other increases the certainty and ease with. which the charge can be exploded, and enables the compound to be exploded by ordinary pow-- der, provided the charge he completely shut in or inclosed between solid walls, (being placed in welltamped blast-holes, for instance.) Such an addition of sulphur is especially advantageous in the case of chlornitro products of heme], toluol, phenol, eresol (eresylic aoid,) and naphthaline with nitrate ofammoniaas the oxygen-yieldingsubstance. The quantity of sulphur to be added is regulated according to the amount ofoxygen available in the oxygenyielding component employed and according to the degree of facility with which the oxygen is given off. ployed as the oxygen-yielding substance, the quantity of sulphur to be added to the explosive mixture amounts to from about three to four per cent, by weight. The quantity of sulphur used may in some cases amount to as much as fifteen per cent. without depriving the compound ofits explosive character. Such largo proportions of sulphur are to be employed in cases where the explosive is required. After the more violent evolution of gas has When nitrate of'potash is em,

to partake more of the character of gunpowder, the action being of a propelling rather :tion is than ofa splitting nature. Wheuuitrate ofaurmonia is used as the oxygen-yielding agent, a

percentage ofsulphnr ampunting to from about one to two per cent. of the total weight of the explosive mixture p revents the blasting-charge from producing an excessively disintegrating and pulverizing action in blasting coal, for example, and diminishes the waste in dust.

The mostadvantageous way of adding the sulphur is to melt it with the chlornitro products, as alrnost'all these substances dissolve more or less sulphur and then retain it uniformly distributed thrpughout the mass when set or stiffened. \Vhen not convenient to melt the materials together,'the sulphiir is to be added to the other ingredients of the blastingmixture in a finely-powdered condition, The said chlornitro products can also be used in combination with simply nitrated aromatic 'co mpoundssuc'n, f orexampl e, as nitro-benzo'l, dinitro-benzol, and the like-and mixed with oxygemyielding substances. This method of employing the chlornitroprodnets is not so suitable for the chlorated and nitrated coa1- tar itself, out is more especially applicable with the chlorated and nitrated compounds of benzol, toluol, phenol, cresol, (cresylic acid,) and naphthaline.

The following are examples of blasting cornpounds of this description:

First. One part diuitro chlorophenol; 05 part uitro-benzol; 0.5 part dinitro-benzol; two parts nitrate of potash; 2.5parts nitrate of amm'onia.

Second. One part .picric acid; one part triiiitro-chlornaphthaline; 2.5 parts nitrate of ammonia; L5 part nitrate of potash.

In the claims I employ the term hyd rocarbons of the aromatic series to cover the class of substances referred to above, including such as henzol, 'toluoi, phenol, cresol, (cresylic 4o acid,) and naphthaliue, whether derived from coal-tar or otherwise,- or even coal-tar itself containing such substances as constituents.

I am well aware that aromatic hydrocarbons have been treated so as to incorporate thereinto 4 5 both chlorine and nitro groups, and I therefore do not claim the processes described for that purpose in this specification; but

What I claim as new, and desire to secure by Letters Patent, is-

1. The new explosive which consists of theconihination of a chlornitro hydrocarburet of the aromatic series with an oxidant, such as a nitrate,.substantially as set forth.

2. The improved explosive consisting of the combination of chlornitro-benzol with an oxidant, such as nitrate of ammonia, substautially asset forth. v

In testimony whereof I have hereunto set my hand in the presence of two subscribing wit- 6o nesscs.

0 ARL ROTH.

Witnesses:

H. SPRINGMA. B. For. 

